Fabrication of Nanostructured Palladium Within Tridentate Schiff-Base-Ligand Coordination Architecture: Enhancement of Electrocatalytic Activity Toward CO2 Electroreduction

Abstract

There has been growing interest in the electrochemical reduction of carbon dioxide (CO2), a potent greenhouse gas and a contributor to global climate change, and its conversion into useful carbon-based fuels or chemicals [1–5]. Numerous homogeneous and heterogeneous catalytic systems have been proposed to induce the CO2 reduction and, depending on the reaction conditions (applied potential, choice of buffer, its strength and pH, local CO2 concentration, or the catalyst used) various products that include carbon monoxide, oxalate, formate, carboxylic acids, formaldehyde, acetone, or methanol, as well as such hydrocarbons as methane, ethane, and ethylene, are typically observed at different ratios. These reaction products are of potential importance to energy technology, food research, medical applications, and fabrication of plastic materials. Given the fact that the CO2 molecule is very stable, its electroreduction processes are characterized by large overpotentials, and they are not energy efficient. To produce highly efficient and selective electrocatalysts, the transitionmetal-based molecular materials are often considered [6–8]. The latter systems are capable of driving multi-electron transfers and, in principle, produce highly reduced species. In reality, such multi-electron charge transfer catalysts tend to effectively induce the two-electron reduction of CO2 to CO rather than yield highly reduced products in large amounts. Metallic copper electrodes are unique in this respect because they can drive multi-electron transfers. Mechanisms of the successful electrochemical reductions of CO2 to methane and ethylene can be interpreted in terms of complex processes occurring at copper electrodes [9, 10]. It is believed that, during electroreduction, the rate limiting step is the protonation of the adsorbed CO product to form the CHO adsorbate [11]. Significant decrease of the reaction overpotentials can be achieved with the use of the metal complex modified electrodes capable of both mediating electron transfers and stabilizing the reduced products [12]. Because reduction of CO2 can effectively occur by hydrogenation [13], in the present work, we concentrate on such a model catalytic system as nanostructured metallic palladium capable of absorbing reactive hydrogen in addition to the ability to adsorb monoatomic hydrogen at the interface [14–16]. Under such conditions, the two-electron reduction of CO2 typically to CO [12] is favored. When the reaction proceeds on palladium in aqueous KHCO3 solutions, carbon monoxide together with hydrogen and small amounts of formate are produced [17–19]. Further, it has been postulated that CO and COOH adsorbates are expected to be formed at the surfaces of Pd electrodes at −1.0 V (vs. Ag/AgCl) and, subsequently, desorbed at even more negative potentials [20]. To produce highly dispersed and stabilized palladium nanoparticles (as for Fig. 1a), we have generated them by electrodeposition (through consecutive potential cycling) from the thin film of N-coordination complex of palladium(II), [Pd(C14H12N2O3)Cl2]2 MeOH. The ligand and its palladium complex (their detailed crystallographic, IR, and NMR features will be a subject of our next publication) were synthesized via typical condensation reaction as published earlier [21, 22]. The resulting metallic Pd nanoparticles (diameters, 5–10 nm), rather than Pd cationic species, are stabilized and activated by nitrogen coordination centers from the macromolecular matrix. Supramolecular architectures of active and well-defined Schiff-base-ligands containing nitrogen donor atoms are of primary importance because A. Wadas : I. A. Rutkowska : P. J. Kulesza (*) Faculty of Chemistry, University of Warsaw, Pasteura 1, 02093 Warsaw, Poland e-mail: pkulesza@chem.uw.edu.pl